Pd(0)-Catalyzed Diastereoselective and Enantioselective Intermolecular Heck–Miyaura Borylation of Internal Enamides for the β‑Aminoboronate Ester Synthesis

Miyaura borylation is widely recognized as one of the most reliable methods for constructing an organoboron compound. Reported herein is Pd(0)-catalyzed asymmetric three-component Heck–Miyaura borylation with the interception of internal olefin, aryldiazonium salt, and diboron reagent. This Heck-triggered borylation protocol proceeds in a highly chemoselective, diastereoselective, and enantioselective manner, thus allowing the expedient construction of 1,2-diaryl substituted β-aminoboronate esters derivatives with vicinal stereogenic centers. The versatility of the resulting benzylic boronic esters allows for their further transformation to more-intricate chiral amines.